Polysiloxane-grafted copolymer topical binder composition with novel fluorochemical comonomer and method of coating therewith

ABSTRACT

A novel composition useful as an adhesive at room temperature (20° C.) and which comprises a copolymer which has both pendant fluorochemical groups and pendant polysiloxane grafts. Also disclosed are topical applications containing the novel composition.

TECHNICAL FIELD

This invention relates to adhesives, surface modifying compositions,sealing compositions, and topical binder compositions comprising acopolymer having a vinyl polymeric backbone with grafted pendantsiloxane polymeric moieties and especially to a method of topicallyapplying such coatings such as to animals.

BACKGROUND ART

Pressure sensitive adhesives and adhesive-coated sheet materials arewell-known in the art as having the ability to adhere toadhesive-receptive surfaces on mere contact. Such coated sheets in theform of labels and tapes, for example, can be adhered to varioussubstrates under very light "finger pressure" and can later be removedtherefrom by stripping the sheet from the surface to which it isattached. It is often desirable to reduce the initial affinity of a PSAfor a substrate while still maintaining sufficient ultimate adhesion(after pressure bonding). The prior art has attempted to achieve thisresult in various ways, mainly by use of different types of "physicalspacers" which have been mixed with or coated on the surface of the PSA.Such spacers act to hold the adhesive slightly away from the substratesurface until the desired placement has been achieved. For example, U.S.Pat. Nos. 3,314,838, 3,331,729, and 3,413,168, all assigned to thepresent assignee, disclose the use of hollow, spheroidal particles ormicroballoons composed of glass, urea- or phenol-formaldehyde resins,etc., to decrease initial adhesion and thereby provide positionability.The microballoons are described as being crushable or collapsible underapplied hand pressure, thereafter enabling the PSA to contact and adhereto the surface of the substrate. Fragments of the collapsed or crushedmicroballoons may, however, remain on the bonding surface of theadhesive rather than completely dispersed into the adhesive layer, andthis may, at least initially, adversely affect the adhesion strength.

Silicone has also been used as a spacing material to reduce the initialadhesion of PSA coatings and thereby produce positionable products. Forexample, U.S. Pat. No. 3,554,835 (Morgan Adhesives Company) discloses amethod of making and using a "slidable" PSA-coated laminate which reliesupon "dots" of silicone or other conventional release material asnon-adhesive spacers to enable initial positioning of the laminate on asubstrate. Similarly, United Kingdom Pat. No. 1,541,311 (UnitedMerchants and Manufacturers, Inc.) describes a PSA-coated laminate wherepositionability is provided by a uniform and discontinuous surfacecoating in the form of small beads or droplets of a non-tackypolysiloxane or polysiloxane-polyoxyalkylene block copolymer. Bothteachings require an additional manufacturing step or steps to apply thesilicone spacing material and to then effect solvent removal, drying, orcuring.

In U.S. Pat. No. 4,151,319 (United Merchants and Manufacturers, Inc.) amethod for making a positionable PSA-coated laminate is disclosedwhereby polysiloxane or polysiloxane-polyoxyalkylene block copolymer isintimately mixed with the PSA itself rather than forming a coating onthe PSA surface. "Pre-mixing" of a siloxane polymer or copolymer in asuitable solvent prior to incorporation into the adhesive isrecommended. Again, the required mixing or dispersing and therecommended pre-mixing contribute additional process steps. The siloxaneadditives of this teaching are said to be in the form of small beads ordroplets dispersed throughout the adhesive mass, and thus some of thedroplets are positioned at the adhesive/release sheet interface of thelaminate (i.e., at the PSA surface) and function to allow initialpositioning on a substrate. The use of either block copolymers or highmolecular weight (above 25,000) polysiloxanes is suggested in UnitedKingdom Pat. No. 1,541,311 and U.S. Pat No. 4,151,319 to minimize lossof adhesive mass, but the resultant laminates still may not offerpredictable levels of positionability even with minor losses.

U.S. Pat. No. 4,346,189 (Morgan Adhesives Company) describes the use ofpolysiloxane additives (of up to about 10,000 molecular weight) in adifferent type of application. The silicones are mixed with tackified,synthetic rubber-based PSA compositions to reduce edge ooze or flow uponcutting of sheets coated with such compositions. Either non-reactive orreactive polysiloxanes can be utilized and are said to appear to adsorbor graft onto other ingredients of the adhesives or take other unknownactions so as to produce the desired effect. It is stated, however, thatthe silicones can be added even at relatively high concentrations (6 to10% solids) without adversely affecting the adhesive characteristics ofthe material.

Graft copolymers, some containing silicone, are being increasingly usedfor general modification of surface properties, as is described in aseries of papers by Y. Yamashita et al., [Polymer Bulletin 7, 289(1982); Polymer Bulletin 10, 368 (1983); Makromol. Chem. 185, 9 (1984);Macromolecules 18, 580 (1985)]. Such use is also reflected in somerecent Japanese art, such as Japanese patent application No. 57-179246,published Nov. 4, 1982, which concerns the use of graft copolymers asadditives to impart long-lasting hydrophobicity (or hydrophilicity) tosurfaces. In Japanese patent application Nos. 58-167606, published Oct.3, 1983, and 58-154766, published Sept. 14, 1983, a method ofpreparation of silicone graft copolymers and the use of these copolymersin coating compositions such as paint films are described. Here, thecopolymers are said to provide long-lasting water- and oil-repellency,stain resistance, and reduced frictional properties. Japanese patentapplication No. 59-78236, published May 7, 1984, discloses a method ofpreparing monofunctional polymeric silicone monomers, i.e.,macromonomers, for use in the preparation of graft copolymers assurface-treatment agents. The use of such silicone macromonomer-graftedcopolymers in coating compositions, again to impart lasting water- andoil-repellency, stain resistance, and low friction characteristics, isdescribed in Japanese patent application No. 59- 126478, published July21, 1984. U.S. Pat. No. 4,728,571, assigned to the present consignee,discloses the use of tack-free polysiloxane-grafted copolymers (andblends thereof with other polymeric materials) as release coatingcompositions for PSA-coated sheet materials and the back side ofPSA-coated tapes.

U.S. Pat. No. 4,693,935 teaches polysiloxane-grafted copolymer pressuresensitive adhesive compositions and sheet materials coated therewith.The invention is directed specifically towards pressure sensitiveadhesives and articles coated therewith.

SUMMARY OF THE INVENTION

The present invention provides a composition which is adhesive at roomtemperature (20° C.) and which comprises a copolymer which has bothpendant fluorochemical groups and pendant polysiloxane grafts. Similarpolymers, but with lower Tg's (glass transition temperatures) anddifferent preferred monomers contain the pendant polysiloxane grafts tocause the exposed surface of a layer of the adhesive composition toinitially have a lower degree of adhesiveness to provide in effect atemporary "low adhesion frontsize". Upon application, however, thependant polysiloxane grafts in the prior art (U.S. Pat. No. 4,693,935)appear to migrate into the body of the layer and the adhering surfacebuilds adhesiveness to form a strong adhesive bond. Thus a temporarychemical surface modification of the pressure-sensitive adhesivecomposition is effected such that positionability of an article bearingthe coating of pressure-sensitive adhesive is possible without many ofthe aforementioned difficulties of the prior art. The present invention,however, utilizes copolymers wherein a slightly different combinationand proportion of monomers is selected so that a variation in thepressure-sensitive characteristics can be provided, and the polymers arefound to have good topical application binding characteristics, as forsurface finishings to glass, ceramics, metal and wood as well as for theapplication of cosmetics and medicaments. The polymers may also be usedas sealing compositions for porous materials such as paper and wood.

Chemical incorporation of the polysiloxane into the copolymers of thepresent invention prevents siloxane loss. Predictable degrees ofsolubility and bondability are thus reliably achieved for a variety ofcompositions.

The non-pressure-sensitive compositions of this invention comprises acopolymer which is inherently non-tacky at 20.0° C. and 0.5 Kg/cm²pressure A Tg of much less than 20.0° C. may of course be sufficient ifthe composition is to be a room temperature pressure-sensitive adhesive.The backbone of the copolymer has grafted to it monovalent siloxanepolymeric moieties having a number average molecular weight above about500 (preferably from about 500 to about 50,000, most preferably fromabout 5,000 to about 25,000).

More specifically, the preferred non-pressure-sensitive adhesivecompositions of the invention comprises the following elements:

(a) the copolymer which comprises repeating A, C, and, B, and optionallyD monomers wherein the composition has a glass transition temperature ofat least 20.0° C., preferably 30.0° C., and most preferably 40.0° C. andwherein:

A is at least one free radically polymerizable acrylic or methacrylicester of a 1,1-dihydroperfluoroalkanol (or homolog thereof, e.g.,fluorinated or non-fluorinated methylene or alkyl homologs),omega-hydridofluoroalkanols, fluoroalkylsulfonamido alcohols, cyclicfluoroalkyl alcohols, and fluoroether alcohols present as at least about0.1% up to about 99% of the total weight of the monomers;

B is at least one reinforcing monomer copolymerizable with A, the amountby weight of B monomer being present as at least about 0.01 to a maximumof 30% of the total weight of all monomers; and

C is a monomer, present as 0.01 to 50% by weight of all monomers, havingthe general formula X(Y)_(n) Si(R)_(3-m) Z_(m) wherein

X is a vinyl group copolymerizable with the A and B monomers;

Y is a divalent linking group (e.g., alkylene, arylene, alkarylene, andaralkylene of 1 to 30 carbon atoms) and incorporating e.g. ester, amide,urethane, urea groups.

n is zero or 1;

m is an integer of from 1 to 3;

R is hydrogen, lower alkyl (e.g., 1 to 4 carbon atoms, methyl, ethyl, orpropyl), aryl (e.g., 6 to 20 carbon atoms, phenyl or substitutedphenyl), or alkoxy (preferably lower alkoxy of 1 to 4 carbon atoms);

Z is a monovalent siloxane polymeric moiety having a number averagemolecular weight above about 500 and is essentially unreactive undercopolymerization conditions;

D is at least one free radically polymerizable acrylate or methacrylatemonomer (hereinafter referred to as "(meth)acrylate" to indicate thatthe methyl portion is optional). Preferably the (meth)acrylate is ahydrocarbon (meth)acrylate indicating that pendant groups other than theacrylate itself are hydrocarbon groups, e.g., alkyl, phenyl,alkylphenyl, phenylalkyl, etc. Examples are the lower to intermediate(C₁ to C₁₂) (meth)acrylic acid esters of alcohols such asisooctylacrylate, isopentylmethacrylate, isobutylmethacrylate,methylmethacrylate, 2-ethylhexylacrylate, isononylmethacrylate, etc.

wherein the monomers are copolymerized to form the polymeric backbonewith the C monomer grafted thereto.

(b) optionally up to about 500 parts of a medicament, or skin or hairsoftening or conditioning ingredient per 10 parts copolymer; and

(c) up to about 500 parts of a compatible solvent or plasticizer per 10parts copolymer.

This invention also provides a process for applying the coatingcomposition to various surfaces such as wood, paper, metal, glass,polymers, and animal bodies comprising the application of thecomposition containing medicaments, conditioning, or softeningingredients to at least a portion of one major surface of a body. Theinvention also provides specific products comprising the compositionwith particular classes of additives.

DETAILED DESCRIPTION OF THE INVENTION

The copolymers of the invention have a well-defined structure, having amethacrylic or acrylic polymeric backbone which has been chemicallymodified by the addition of pendant flurochemical groups and by a smallweight percentage of polysiloxane grafts. When such copolymers arecoated on an exposed area of an animal body or on animal hair, non-tackycoatings or localized applications can be aesthetically and comfortablymade on those bodies. Once applied to a surface, the composition canmaintain the presence of active ingredients applied in the composition.

The surface characteristics of the copolymeric adhesive composition canbe chemically tailored through variation of both the molecular weight ofthe grafted siloxane polymeric moiety and the total siloxane content(weight percentage) of the copolymer, with higher siloxane contentand/or molecular weight providing lower initial adhesion. The chemicalnature and the molecular weight of the (meth)acrylic polymeric backboneof the copolymer can also be chosen such that the level of adhesion tothe substrate can be matched to the requirements of a particularapplication. Since their siloxane content is relatively low, thecopolymers of this invention are readily compatible with siloxane-freepolymers, for example polymers of composition similar to that of thevinyl or methacrylic backbone.

The preferred method of preparation of the compositions of thisinvention provides graft copolymer of high purity which can be coateddirectly from the polymerization solvent, if necessary or desired. Theresultant coatings do not require curing or crosslinking. However, ifenhancement of either shear strength or resistance to solvents orphotochemical or oxidative forces is desired, crosslinking may beeffected by standard methods well-known in the art, such as radiationcuring (electron beam or ultraviolet light) or chemical crosslinking.

The siloxane polymeric moieties can be grafted by polymerizing monomeronto reactive sites located on the backbone, by attaching preformedpolymeric moieties to sites on the backbone, or, preferably, bycopolymerizing the acrylic or methacrylic monomer(s), A, and, polarmonomer(s), B, with preformed polymeric siloxane monomer, C. Since thepolymeric siloxane surface modifier is chemically bound, it is possibleto chemically tailor the compositions of this invention such that aspecific degree of cohesiveness and solubility are provided and can bereproduced with consistency.

As previously mentioned, the composition of this invention comprises a(meth)acrylate copolymer which is inherently non-tacky at roomtemperature (20.0° C.) and moderate pressure (0.5 Kg/cm²). Monovalentsiloxane polymeric moieties having a number average molecular weightabove about 500 are grafted to the copolymer backbone. The copolymerpreferably consists essentially of copolymerized repeating units from A,B, and C monomers and, optionally, D monomers according to thedescription given above.

The A monomer or monomers (there may be more than one) are chosen suchthat a non-tacky material is obtained upon polymerization of A (or A andB). Representative examples of A monomers are acrylic or methacrylicacid esters of 1,1-dihydroperfluoroalkanols (1) and homologs (2),

    ______________________________________                                        1 CF.sub.3 (CF.sub.2).sub.x CH.sub.2 OH                                                             where x is zero to                                      2 CF.sub.3 (CF.sub.2).sub.x (CH.sub.2).sub.y OH                                                     20 and y is at                                                                least 1 up to 10                                        w-hydrofluoroalkanols 3,                                                      3 HCF.sub.2 (CF.sub.2).sub.x (CH.sub.2).sub.y OH                                                    where x is 0 to 20                                                            and y is at least                                                             1 up to 10                                              fluoroalkylsulfonamido alcohols 4,                                             ##STR1##             where x is zero to 20 and R.sup.1 is alkyl or                                 arylalkyl of up to 20 carbon atoms or cycloalkyl of                           up to 6 ring carbon atoms                               cyclicfluoroalkyl alcohols 5,                                                  ##STR2##             where z is zero to 7 and y is at least 1 up to 10       6 CF.sub.3 (CF.sub.2 CF.sub.2O) .sub.q(CF.sub.2 O).sub.x (CH.sub.2).sub.y     OH                    where q is 2 to 20 and                                                        greater than x, x is 0                                                        to 20, and y is at                                                            least 1 up to 10                                         ##STR3##             where p and s are at least 1 and r is 1 to              ______________________________________                                                              6                                                   

Preferred polymerized A monomer backbone compositions include polymersof fluoroacrylates 8-13. ##STR4##

Representative examples of polar monomer, B, include acrylic acid,methacrylic acid, itaconic acid, acrylamide, methacrylamide,N,N-dimethylacrylamide, acrylonitrile, methacrylonitrile, and N-vinylpyrrolidone. The hydrophilic `B` monomers may be mono- ormultifunctional hydroxy group containing molecules represented by thegeneral formula:

    CH.sub.2 ═CR.sup.2 --CO--L--R.sup.3 --(OH).sub.d

where R² =H, methyl, ethyl, cyano or carboxymethyl, L=0, NH, d=1-3 andR³ is a hydrocarbyl radical of valence d+1 containing from 1-12 carbonatoms. The preferred monomers in this class are hydroxyethyl(meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl(meth)acrylate, glycerol mono(meth)acrylate, tris(hydroxymethyl)ethanemonoacrylate, pentaerythritol mono(meth)acrylate, N-hydroxymethyl(meth)acrylamide, hydroxyethyl (meth)acrylamide and hydroxypropyl(meth)acrylamide.

The hydrophilic monomer `B` may belong to the class of mono- ormultifunctional amino group containing molecules of the general formula:

    CH.sub.2 ═CR.sup.2 --CO--L--R.sup.3 --(NR.sup.4 R.sup.5).sub.d

where R²,L, R³, and d are as defined above and R⁴ and R⁵ are H or alkylgroups of 1-12 carbon atoms or together they constitute a cyclic orheterocyclic group. Preferred monomers of this class are aminoethyl(meth)acrylate, aminopropyl (meth)acrylate, N, N-dimethylaminoethyl(meth)acrylate, N,N-diethylaminoethyl (meth)acrylate,N,N-dimethylaminopropyl (meth)acrylamide, N-isopropylaminopropyl(meth)acrylamide and 4-methyl-1-acryloyl-piperazine.

The hydrophilic `B` monomers may also be alkoxy substituted(meth)acrylates or (meth)acrylamides such as methoxyethyl(meth)acrylate, 2(2-ethoxyethoxy)ethyl (meth)acrylate, polyethyleneglycol mono(meth)acrylate or polypropylene glycol mono(meth)acrylate.

Particularly useful are `B` monomers that have substituted orunsubstituted ammonium groups of the general formula:

    CH.sub.2 ═CR.sup.2 --CO--L--R.sup.3 --(NR.sup.4 R.sup.5 R.sup.6).sub.d Q.sup.-

where R², R³, R⁴, R⁵, L and d are as defined above and R⁶ is H or alkylof 1-12 carbon atoms and Q⁻ is an organic or inorganic anion. Preferredexamples of such monomers are 2-N,N,N-trimethylammonium ethyl(meth)acrylate, 2-N,N,N-triethylammonium ethyl (meth)acrylate,3-N,N,N-trimethylammonium propyl (meth)acrylate,N(2-N',N',N'-trimethylammonium) ethyl (meth)acrylamide, N-(dimethylhydroxyethyl ammonium) propyl (meth)acrylamide etc. where the counterionmay be chloride, bromide, acetate, propionate, laurate, palmitate,stearate etc. The monomer can also be N,N-dimethyl diallyl ammonium saltof an organic or inorganic counterion.

Ammonium group containing polymers can also be prepared by using as the`B` monomer, any of the amino group containing monomer described above,and acidifying the resultant polymers with organic or inorganic acid toa pH where the pendant amino groups are substantially protonated.Totally substituted ammonium group containing polymers may be preparedby alkylating the above described amino polymers with alkylating groups,the method being commonly known in the art as the Menschutkin reaction.

The hydrophilic `B` monomers of the invention can also be sulfonic acidgroup containing monomers e.g. vinyl sulfonic acid, styrene sulfonicacid, 2-acrylamido-2-methyl propane sulfonic acid, allyloxybenzenesulfonic acid etc. These monomers may be used in the protonated acidform as monomers and the corresponding polymers obtained may beneutralized with an organic and inorganic base to give the salt form ofthe polymers.

The hydrophilic `B` monomers can be other alkenyl heterocycles such asvinyl pyridines, vinyl imidazoles, vinyl benzimidazoles, vinylazlactones, vinyl furans etc. These heterocyclic comonomers providesites for hydrogen bonding with polar substrates and improve adhesion ofthe resultant polymers to such substrates.

Preferred B monomers are acrylic acid, N,N-dimethyl acrylamide,methacrylic acid, and N-vinyl pyrrolidone. The amount by weight of Bmonomer preferably does not exceed about 30% of the total weight of allmonomers such that excessive firmness of the polymer is avoided.Incorporation of B monomer to the extent of about 2% to about 25% byweight is most preferred and provides compositions of high cohesive orinternal strength, good adhesion to polar surfaces and which alsoretains good physical properties.

The preferred C monomer may be further defined as having an X groupwhich has the general formula ##STR5## wherein R⁷ is a hydrogen atom ora COOH group and R⁸ is a hydrogen atom, a methyl group, or a CH₂ COOHgroup.

The Z group of the C monomer has the general formula ##STR6## where R⁹and R¹¹ are independently lower alkyl, aryl, or fluoroalkyl, where loweralkyl and fluoroalkyl both refer to alkyl groups having from one tothree carbon atoms and where aryl refers to phenyl or substituted phenyl(of up to 20 carbon atoms). R¹⁰ may be alkyl (of 1 to 20 carbon atoms),alkoxy (of 1 to 20 carbon atoms), alkylamino (of 1 to 20 carbon atoms),aryl (of up to 20 carbon atoms), hydroxyl, or fluoroalkyl (of 1 to 20carbon atoms), and e is an integer from about 5 to about 700.Preferably, the C monomer has a general formula selected from the groupconsisting of the following, where m is 1, 2, or 3, g is zero or 1, R"may be alkyl (of 1 to 10 carbon atoms) or hydrogen, f is an integer from2 to 6, h is an integer from zero to 2, and X, R, and Z are as definedabove: ##STR7##

The topical composition of this invention is provided by copolymerizingthe A, B and C, and, optionally, D monomers followed, when necessary ordesirable, by blending with a compatible cosmetic or medicinally activeingredient in order to optimize the ultimate utile properties of thecomposition.

When the above described composition is coated on skin or hair in properproportions in a composition, no tackiness is observed when thecomposition is dry. Copolymers containing C monomer having a molecularweight less than about 500 are not very effective in providingsubstantivity, or persistant retention on the skin. Copolymerscontaining C monomer having a molecular weight greater than 50,000effectively provide substantivity, but, at such high molecular weights,possible incompatibility of the C monomer with the remaining monomerduring the copolymerization process may result in reduced incorporationof C. A molecular weight of C monomer ranging from about 500 to about50,000 is therefore preferred. A molecular weight range from about 5,000to about 25,000 is most preferred.

The C monomer is preferably incorporated in the copolymer in the amountof about 0.01 to about 50% of the total monomer weight to obtain thedesired properties. The amount of C monomer included may vary dependingupon the particular application, but incorporation of such percentagesof C monomer having a molecular weight in the above-specified range hasbeen found to proceed smoothly and to result in material which provideseffective substantivity for a variety of applications while still beingcost effective.

The total weight of B and C monomers is preferably within the range ofabout 0.01 to about 70% of the total weight of all monomers in thecopolymer.

The C monomers of this invention are terminally functional polymershaving a single functional group (the vinyl, ethylenically unsaturated,acryloyl, or methacryloyl group) and are sometimes termed macromonomersor "macromers". Such monomers are known and may be prepared by themethod disclosed by Milkovich et. al., as described in U S. Pat. Nos.3,786,116 and 3,842,059. The preparation of polydimethylsiloxanemacromonomer and subsequent copolymerization with vinyl monomer havebeen described in several papers by Y. Yamashita et al., [Polymer J. 14,913 (1982); ACS Polymer Preprints 25 (1), 245 (1984); Makromol. Chem.185, 9 (1984)]. This method of macromonomer preparation involves theanionic polymerization of hexamethylcyclotrisiloxane monomer (D₃) toform living polymer of controlled molecular weight, and termination isachieved via chlorosilane compounds containing a polymerizable vinylgroup. Free radical copolymerization of the monofunctional siloxanemacromonomer with vinyl monomer or monomers provides siloxane-graftedcopolymer of well-defined structure, i.e., controlled length and numberof grafted siloxane branches.

Suitable monomers for use in the above mentioned anionic polymerizationare, in general, diorganocyclosiloxanes of the formula ##STR8## where R⁹and R¹¹ are as previously defined and where e is an integer of 3 to 7.Preferred are the cyclic siloxanes where e is 3 or 4 and R⁹ and R¹¹ areboth methyl, these cyclic siloxanes being hereafter designated D₃ andD₄, respectively. D₃, which is a strained ring structure, is especiallypreferred.

Initiators of the anionic polymerization are chosen such thatmonofunctional living polymer is produced. Suitable initiators includealkali metal hydrocarbons such as alkyl or aryl lithium, sodium, orpotassium compounds containing up to 20 carbon atoms in the alkyl oraryl radical or more, preferably up to 8 carbon atoms. Examples of suchcompounds are ethylsodium, propylsodium, phenylsodium, butylpotassium,octylpotassium, methyllithium, ethyllithium, n-butyllithium,sec-butyllithium, tert-butyllithium, phenyllithium, and2-ethylhexyllithium. Lithium compounds are preferred as initiators. Alsosuitable as initiators are alkali metal alkoxides, hydroxides, andamides, as well as triorganosilanolates of the formula ##STR9## where Mis alkali metal, tetraalkylammonium, or tetraalkylphosphonium cation andwhere R⁹, R¹⁰, and R¹¹ are as previously defined. The preferredtriorganosilanolate initiator is lithium trimethylsilanolate (LTMS). Ingeneral, the preferred use of both strained cyclic monomer and lithiuminitiator reduces the likelihood of redistribution reactions and therebyprovides siloxane macromonomer of narrow molecular weight distributionwhich is reasonably free of unwanted cyclic oligomers.

Molecular weight is determined by the initiator/cyclic monomer ratio,and thus the amount of initiator may vary from about 0.004 to about 0.4mole of organometallic initiator per mole of monomer. Preferably, theamount will be from about 0.008 to about 0.04 mole of initiator per moleof monomer.

For the initiation of the anionic polymerization, an inert, preferablypolar organic solvent can be utilized. Anionic polymerizationpropagation with lithium counterion requires either a strong polarsolvent such as tetrahydrofuran, dimethyl sulfoxide, orhexamethylphosphorous triamide, or a mixture of such polar solvent withnonpolar aliphatic, cycloaliphatic, or aromatic hydrocarbon solvent suchas hexane, heptane, octane, cyclohexane, or toluene. The polar solventserves to "activate" the silanolate ion, making propagation possible.

Generally, the polymerization can be carried out at a temperatureranging from about -50° C. to about 100° C., preferably from about -20°C. to about 30° C. Anhydrous conditions and an inert atmosphere such asnitrogen, helium, or argon are required.

Termination of the anionic polymerization is, in general, achieved viadirect reaction of the living polymeric anion with halogen-containingtermination agents, i.e., functionalized chlorosilanes, to producevinyl-terminated polymeric monomers. Such terminating agents may berepresented by the general formula X(Y)_(n) Si(R)_(3-m) Cl_(m), where mis 1, 2, or 3 and where X, Y, n, and R have been previously defined. Apreferred terminating agent is methacryloxypropyldimethylchlorosilane.The termination reaction is carried out by adding a slight molar excessof the terminating agent (relative to the amount of initiator) to theliving polymer at the polymerization temperature. According to theaforementioned papers by Y. Yamashita et al., the reaction mixture maybe ultrasonically irradiated after addition of the terminating agent inorder to enhance functionality of the macromonomer. Purification of themacromonomer can be effected by addition of methanol.

Representative examples of D monomers may comprise (up to 50% of allmonomers) the lower to intermediate methacrylic acid esters of alcoholssuch as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol,1,1-dimethyl ethanol, 2-methyl-1-propanol, 1-pentanol, 2-pentanol,3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-hexanol,2-methyl-1-pentanol, 3-methyl-1-pentanol, cyclohexanol,2-ethyl-1-butanol, 3-heptanol, benzyl alcohol, 2-octanol,6-methyl-1-heptanol, 2-ethyl-1-hexanol, 3,5-dimethyl-1-hexanol,3,5,5-trimethyl-1-hexanol, 1-decanol, and 1-dodecanol, and the like, thealcohols having from 1 to 12 carbon atoms, preferably 1 to 8 carbonatoms, with the average number of carbon atoms being about 4-12.Preferably non-tertiary alcohols are used. Some small amount ofcopolymerizable styrene, vinyl esters, vinyl chloride, vinylidenechloride, acryloyl monomers and the like may be used. These comonomersmust not prevent the maintainance of a Tg of at least 20.0° C. in thefinal polymeric composition preferably 30.0° C., and more preferably atleast 40.0° C. Such monomers are known in the art, and many arecommercially available. Preferred polymerized D monomer backbonecompositions include poly(isooctyl methacrylate), poly(isononylmethacrylate), poly(2-ethylhexyl methacrylate),polyisopentylmethacrylate, poly(n-butyl methacrylate), poly(isobutylmethacrylate), poly(methylmethacrylate), and copolymers thereof withother D monomer or monomers. Some amount of acrylate may also bepresent, but only in such amounts that these compositions are notpressure sensitive.

The copolymerization of the A monomer, B monomer and C monomer andoptionally D monomer is carried out by conventional free radicalpolymerization such as described by Ulrich, U.S. Reissue Pat. No.24,906. The monomers are dissolved in an inert organic solvent andpolymerized utilizing a suitable free radical initiator which can beeither thermally or photochemically activated. Suitable thermallyactivated initiators include azo compounds such as 2,2'-azobis(isobutyronitrile), hydroperoxides such as tert-butyl hydroperoxide, andperoxides such as benzoyl peroxide or cyclohexanone peroxide, andsuitable photochemically activated initiators include benzophenone,benzoin ethyl ether, and 2,2-dimethoxy-2-phenyl acetophenone. The amountof initiator used is generally about 0.01 to about 5% by weight of thetotal polymerizable composition.

The organic solvent used in the free radical copolymerization can be anyorganic liquid which is inert to the reactants and product and whichwill not otherwise adversely affect the reaction. Suitable solventsinclude ethyl acetate and mixtures such as ethyl acetate with toluene orheptane with toluene and isopropyl alcohol. Other solvent systems mayalso be used. The amount of solvent is generally about 30-80% by weightof the total weight of reactants and solvent. In addition to solutionpolymerization, the copolymerization can be carried out by otherwell-known techniques such as suspension, emulsion, and bulkpolymerization.

As described above, the preferred grafting technique involvescopolymerization of methacrylic monomer, A, reinforcing monomer, B, andchemically tailored macromonomer, C, of controlled molecular weight andoptionally monomer D. Other grafting techniques can be employed, eachproviding a degree of predictability of the properties of the endproduct. One alternative technique involves preforming the methacrylicpolymeric backbone, then copolymerizing this preformed backbone withcyclic siloxane monomer. Another approach is to graft preformedmonofunctional siloxane polymer to a preformed methacrylic polymericbackbone. These and other polymer grafting techniques are described byNoshay and McGrath in Block Copolymers, Academic Press, New York (1977),pages 13-16 and in greater detail by Battaerd and Tregear in GraftCopolymers, J. Wiley and Sons, New York (1967).

The copolymeric, topically applied, compositions of this invention insolution or dispersion are easily coated upon suitable body areas butnot areas of the primary integumentary system, e.g., hair on the scalp.The compositions maybe used on areas with vestigial hair (such as theface and arms and legs) but are not intended in the practice of theinvention as primary treatments for hair. They are also not preferredfor treatments in the lining of the eye or nasal passage. Non-mucosalareas of the body of non-aqueous dwelling mammals are particularlypreferred and fur treatments for non-human animals are also preferred(dogs, cats, rabbits, etc.). The compositions with other appropriateadditives may be used as adhesives, conditioning treatments for organicor inorganic surfaces, and sealants for wood or paper.

The compositions of this invention may be coated by any of a variety ofconventional coating techniques such as wiping, spraying, handspreading, swab application, and the like.

The topical application of medicaments to the skin has traditionallybeen done with the application of self-sustaining or self-supportingcohesive articles such as films, tapes, or plasters as a proposedimprovement over direct applications of powders, ointments, creams,lotions or the like. It has been felt that these more substantial mediaprovided a longer lasting and more controllable application of medicineto the skin or hair of a mammal. These medical applications suffer fromdistinct problems of their own, however. All of the films and tapes tendto be uncomfortable as they cannot completely conform with stretching,bending, or wrinkling which the exterior surfaces of bodies undergoduring movement. The films, tapes and plasters are not cosmeticallyacceptable, especially if applied to the face and hands, which areexposed to view. Films and tapes are easily and accidentally removed, inpart or in whole, from the skin by inadvertent contact or perspirationoccurring under the film or tape. This directly reduces the medicalefficiency of the application. Films and tapes can trap moisture againstthe surface which can be medically disadvantageous and can block oxygenpenetration to the surface. The application of thin polymer films willnot solve these problems because the films can be readily broken anddelivery of the medicine can be interrupted.

It has been found in the present invention that by selecting onlyappropriate proportions of medicaments and the non-pressure-sensitiveadhesive polymeric binders in solutions, emulsions, or dispersions thatan extremely effective topical application of medicaments, and skintreatments, and fur of hair treatments for animals other than humans maybe performed. The proportions are selected, contrary to conventionalwisdom, so that a non-cohesive, non-tacky coating of the binder andmedicament is formed on the skin particularly in non-mucosal areas.

Medicaments according to the practice of the present invention are thosecompounds or materials which have a direct medicinal or neurologicaleffect (excluding alcohols). Materials which have a beneficial activityagainst the growth, propogation or survival of bacteria, fungi, orviruses or which are antihistamines, antitoxins, anaesthetics,analgesics, antipruritics, vitamins, and antiinflammatants are includedin the term medicaments. These materials are well known in the medicalart and no exhaustive list is thought to be necessary. Exemplarycompounds include hydrocortisone acetate, undecylenic acid, tolnaftate,methyl salicylate, lidocaine, oxytetracycline.HCl, retinoic acid,Minoxidil®, etc. These medicaments may provide the medicinal activity atthe site of application or upon absorption through the skin.

These medicaments are combined in the critical proportions of thisinvention with the oil compatible non-pressure sensitive adhesives.Pressure-sensitive adhesives are art recognized as a standard class ofmaterials. These are adhesives which in dry (substantially solvent freeexcept for residual solvent) form are aggressively and permanently tackyat room temperature (e.g., 15.0° to 25.0° C.) and firmly adhere to avariety of dissimilar surfaces upon mere contact without the need formore than manual pressure. They require no activation by water, solventor heat in order to exert a strong adhesive holding force towards suchmaterials as paper, cellophane, glass, wood and metals. They have asufficiently cohesive holding and elastic nature so that, despite theiraggressive tackiness, they can be handled with the fingers and removedfrom smooth surfaces without leaving a substantial residue (cf. TestMethod for Pressure-Sensitive Tapes, 6th Ed., Pressure Sensitive TapeCouncil, 1953). Pressure-sensitive adhesives and tapes are well known,and the wide range and balance of properties desired in such adhesiveshas been well analyzed (cf. U.S. Pat. No. 4,374,883; and"Pressure-Sensitive Adhesives" in Treatise on Adhesion and AdhesivesVol. 2, "Materials", R. I. Patrick, Ed., Marcel Dekker, Inc., N.Y.,1969). The various materials and compositions useful aspressure-sensitive adhesives are available commercially and arethoroughly discussed in the literature (e.g., Houwink and Salomon,Adhesion and Adhesives, Elsevier Publ. Co., Amsterdam, Netherlands,1967; Handbook of Pressure-Sensitive Adhesive Technology, Donates Satas,Ed., VanNostrand Reinhold Co., N.Y., 1982).

Pressure-sensitive adhesives are generally chemically composed ofrubber-resin materials, acrylic resins, polyurethane resins, siliconeresins, and the like. Among the various patent literature describingcompositions and improvements in pressure-sensitive adhesiveformulations are U.S. Reissue Pat. No. 24,906; U.S. Pat. Nos. 2,652,351;3,740,366; 3,299,010; 3,770,708; 3,701,758; 3,922,464; 3,931,087;4,012,560; 4,077,926; 4,387,172; 4,418,120; 4,629,663; and the like.These classes of rubber resin, acrylic, silicone and polyurethanepressure-sensitive adhesives as well as any other pressure-sensitiveadhesives are not generally useful in the present invention. Onlynon-pressure sensitive adhesives are used in the detailed proportions ofthe present invention, and non-tacky applications of medicaments areprovided. The polymers useful in the present invention are oilcompatible (dispersible, swellable, or soluble in organic oils andnon-polar solvents) and generally are clearly hydrophobic in theirproperties.

The molecular weight of the polymers used in the compositions may varyover a broad range. The molecular weight must be suitably large toprovide the requisite binding effect. The upper limit is determined onlyby formulation requirements. As the molecular weight increases, thepolymers tend to become too viscous to formulate easily intocosmetically-appealing compositions. Generally, polymers having aBrookfield viscosity between 50 and 100,000 cps and preferably between500 and 15,000 cps, when measured at 16.6 percent non-volatiles, will beuseful in the compositions of the invention.

The acrylate polymers useful in the compositions may be insoluble inwater and may have a solubility parameter between about 6 and 10 inpoorly and moderately hydrogen bonding solvents. The method fordetermining solubility parameter ranges of polymers and an extensivelist of solvents (classified as either poorly hydrogen bonding,moderately hydrogen bonding, or strongly hydrogen bonding) are describedin Polymer Handbook (edited by Bandrup and Immergut), pages IV-344-358.Acrylate polymers having the requisite solubility parameter will besoluble, swellable or dispersible in the oil base of the compositions.

The compositions of the invention are of three basic types, i.e., oils,water-in-oil and oil-in-water emulsions. The oil formulations areprepared by mixing the oil base, polymer and active ingredient (e.g.,medicament) together and warming the mixture with slow agitation toabout 140° F. The water phase ingredients, if part of an emulsionformulation, are combined and heated to 180° F. This phase is slowlyadded to the oil phase ingredients, also at 180° F., and the combinationallowed to cool with agitation. The formulations generally contain about0.5 to 10 percent by weight of the acrylate polymer, with the preferredrange being from about 0.5 to 5.0 percent by weight. At levels below0.25 percent, the polymer is less effective in holding a significantamount of the active ingredient (e.g., medicament) on the skin when theskin is exposed to water. At levels above 10 percent, the formulationgenerally becomes sticky and develops an unpleasant feeling.

The cosmetic oil base, if any, of the compositions may be solid orliquid, but the entire formulation should be somewhat fluid at skintemperatures for ease of application. Fragrances, fillers, dyes,colorants, preservatives, antioxidants and other such material may beincluded in minor amounts in the compositions without affecting thesubstantivity of the composition.

When applied to human skin, these products form films of the medicamenton the skin surface. The polymer dispersed therein holds the medicamentor chemical treatment onto the skin so that a significantly greaterpharmacological or cosmetic benefit is provided than the compositionswithout the polymer.

As indicated above, the composition to be applied to topical areas ofmammals (generally non-water dwelling mammals) comprises 0.25-10% bytotal weight of polymer, preferably 0.5 to 5 percent by weight, and mostpreferably 0.5 to 2% by weight of polymer per total weight ofcomposition. The active ingredient or medicament may be present in abroader weight range of 0.1 to 50% by total weight of the composition,preferably 0.25 to 20% by weight, more preferably 0.5 to 10% and mostpreferably 1 to 3% by weight. The ratio of the polymer to medicament(wt. polymer/wt. medicament) should also be in the range of 1/5 to 1/50to achieve the benefits of the present invention.

These and other aspects of the invention will be shown in the followingnon-limiting examples.

EXAMPLE 1

Polymerization of methacryloxypropyl-terminated polydimethylsiloxanemacromonomer (PDMS) with N,N-dimethylacrylamide (DMA) and2(N-methylperfluorooctane sulfonamido)ethyl methacrylate (MeFOSEMA).

To a mixture of 20 parts of PDMS (MW=20,000), 20 parts of DMA and 60parts of MeFOSEMA in 200 parts of ethyl acetate and 10 parts ofisopropanol was added 0.5 parts of benzoyl peroxide (BPO). This solutionwas purged with nitrogen and sealed in a bottle under a nitrogenatmosphere. The bottle was heated in an Atlas Launder-0-Meter® at 60° C.for 48 hours and the polymer was recovered by evaporation of solventunder reduced pressure.

EXAMPLES 2-4

Polymerization of methacryloxypropyl-terminated polydimethylsiloxanemacromonomer (PDMS) with N,N-dimethylacrylamide (DMA), isobutylmethacrylate (IBM) and 2(-N-methyl perfluorooctane sulfonamido)ethylmethacrylate (MeFOSEMA).

To a mixture of 20 parts of PDMS (MW=20,000), 20 parts of DMA, 14-45parts of IBM, 15-45 parts of MeFOSEMA in 200 parts of ethyl acetate and10 parts of isopropanol was added 0.5 parts of benzoyl peroxide (BPO).This solution was purged with nitrogen and sealed in a bottle under anitrogen atmosphere. The bottle was heated in a Launder-O-Meter® at 60°C. for 48 hours and the polymer was recovered by evaporation of solventunder reduced pressure.

    ______________________________________                                        Example   PDMS    DMA       IBM  MeFOSEMA                                     ______________________________________                                        2         20      20        45   15                                           3         20      20        30   30                                           4         20      20        15   45                                           ______________________________________                                    

EXAMPLE 5

Polymerization of methacryloxypropyl-terminated polydimethylsiloxanemacromonomer (PDMS) with N,N-dimethylacrylamide (DMA), isobutylmethacrylate (IBM) and 1,1-dihydro perfluorooctyl methacrylate (FOMA).

To a mixture of 20 parts of PDMS (MW=20,000), 20 parts of DMA, 30 partsof IBM and 30 parts of FOMA in 200 parts of ethyl acetate and 10 partsof isopropanol was added 0.5 parts of benzoyl peroxide (BPO). Thissolution was purged with nitrogen and sealed in a bottle under anitrogen atmosphere. The bottle was heated in a Launder-O-Meter® at 60°C. for 48 hours and the polymer was recovered by evaporation of solventunder reduced pressure.

EXAMPLE 6

Polymerization of methacryloxypropyl-terminated polydimethylsiloxanemacromonomer (PDMS) with N,N-dimethylacrylamide (DMA), isobutylmethacrylate (IBM) and 2(N-butyl perfluorooctane sulfonamido)ethylacrylate (BuFOSEA).

To a mixture of 20 parts of PDMS (MW=20,000), 20 parts of DMA, 30 partsof IBM and 30 parts of BuFOSEA in 200 parts of ethyl acetate and 10parts of isopropanol was added 0.5 parts of benzoyl peroxide (BPO). Thissolution was purged with nitrogen and sealed in a bottle under anitrogen atmosphere. The bottle was heated in a Launder-O-Meter® at 60°C. for 48 hours and the polymer was recovered by evaporation of solventunder reduced pressure.

EXAMPLE 7

Polymerization of methacryloxypropyl-terminated polydimethylsiloxanemacromonomer (PDMS) with acrylic acid (AA), isobutyl methacrylate (IBM)and 2-(N-methyl perfluorooctane sulfonamido)ethyl methacrylate(MeFOSEMA).

To a mixture of 20 parts of PDMS (MW=20,000), 10 parts of AA, 60 partsof IBM and 10 parts of MeFOSEMA in 200 parts of ethyl acetate and 10parts of isopropanol was added 0.5 parts of benzoyl peroxide (BPO). Thissolution was purged with nitrogen and sealed in a bottle under anitrogen atmosphere. The bottle was heated in a Launder-O-Meter® at 60°C. for 48 hours and the polymer was recovered by evaporation of solventunder reduced pressure.

EXAMPLE 8

Polymerization of methacryloxypropyl-terminated polydimethylsiloxanemacromonomer (PDMS) with N-vinyl pyrrolidone (NVP), isobutylmethacrylate (IBM) and 2(N-methyl perfluorooctane sulfonamido)ethylmethacrylate (MeFOSEMA).

To a mixture of 20 parts of PDMS (MW=20,000), 20 parts of NVP, 30 partsof IBM and 30 parts of MeFOSEMA in 200 parts of ethyl acetate and 10parts of isopropanol was added 0.5 parts of benzoyl peroxide (BPO). Thissolution was purged with nitrogen and sealed in a bottle under anitrogen atmosphere. The bottle was heated in a Launder-O-Meter® at 60°C. for 48 hours and the polymer was recovered by evaporation of solventunder reduced pressure.

EXAMPLE 9

Polymerization of methacryloxypropyl-terminated polydimethylsiloxanemacromonomer (PDMS) with N-vinyl pyrrolidone (NVP), isobutylmethacrylate (IBM) and 2(N-butyl perfluorooctane sulfonamido)ethylacrylate (BuFOSEA).

To a mixture of 20 parts of PDMS (MW=20,000), 20 parts of NVP, 30 partsof IBM and 30 parts of BuFOSEA in 200 parts of ethyl acetate and 10parts of isopropanol was added 0.5 parts of benzoyl peroxide (BPO). Thissolution was purged with nitrogen and sealed in a bottle under anitrogen atmosphere. The bottle was heated in a Launder-O-Meter at 60°C. for 48 hours and the polymer was recovered by evaporation of solventunder reduced pressure.

EXAMPLE 10

Polymerization of methacryloxypropyl-terminated polydimethylsiloxanemacromonomer (PDMS) with N-vinyl pyrrolidone (NVP), isobutylmethacrylate (IBM) and 1,1-dihydro perfluorooctyl methacrylate (FOMA).

To a mixture of 20 parts of PDMS (MW=20,000), 20 parts of NVP, 30 partsof IBM and 30 parts of FOMA in 200 parts of ethyl acetate and 10 partsof isopropanol was added 0.5 parts of benzoyl peroxide (BPO). Thissolution was purged with nitrogen and sealed in a bottle under anitrogen atmosphere. The bottle was heated in a Launder-O-Meter® at 60°C. for 48 hours and the polymer was recovered by evaporation of solventunder reduced pressure.

EXAMPLE 11

Polymerization of methacryloxypropyl-terminated polydimethylsiloxanemacromonomer (PDMS) with 2-vinyl-4,4-dimethyl-1,3-oxazolin-5-one (VDM),isobutyl methacrylate (IBM) and 2(N-methyl perfluorooctanesulfonamido)ethyl methacrylate (MeFOSEMA).

To a mixture of 20 parts of PDMS (MW=20,000), 20 parts of VDM, 30 partsof IBM and 30 parts of MeFOSEMA in 200 parts of ethyl acetate and 10parts of isopropanol was added 0.5 parts of benzoyl peroxide (BPO). Thissolution was purged with nitrogen and sealed in a bottle under anitrogen atmosphere. The bottle was heated in a Launder-O-Meter® at 60°C. for 48 hours and the polymer was recovered by evaporation of solventunder reduced pressure.

EXAMPLE 12

Polymerization of methacryloxypropyl-terminated polydimethylsiloxanemacromonomer (PDMS) with N-vinyl pyrrolidone (NVP),2-vinyl-4,4-dimethyl-1,3-oxazolin-5-one (VDM), isobutyl methacrylate(IBM) and 2(N-methyl perfluorooctane sulfonamido)ethyl methacrylate(MeFOSEMA).

To a mixture of 20 parts of PDMS (MW=20,000), 15 parts of NVP, 5 partsof VDM, 30 parts of IBM and 30 parts of MeFOSEMA in 200 parts of ethylacetate and 10 parts of isopropanol was added 0.5 parts of benzoylperoxide (BPO). This solution was purged with nitrogen and sealed in abottle under a nitrogen atmosphere. The bottle was heated in aLaunder-O-Meter® at 60° C. for 48 hours and the polymer was recovered byevaporation of solvent under reduced pressure.

EXAMPLE 13

Polymerization of 10,000 MW methacryloxypropyl-terminatedpolydimethylsiloxane macromonomer (PDMS) with N-vinylpyrrolidone (NVP),methyl methacrylate (MMA), and 1,1-dihydroperfluorooctyl methacrylate(FOMA).

To a mixture of 20 parts of PDMS, 60 parts of MMA, 10 parts of NVP, and10 parts of FOMA in 1000 parts of cyclohexane was added 0.16 parts ofazobis(isobutyronitrile). The solution was placed in a 150 ml 3-neckflask fitted with a reflux condensor, a mechanical stirrer, and athermometer. The flask was flushed with nitrogen gas and the solutionwas heated to 55° C. for 20 hours. The resultant polymer formed a solidmass which was not soluble in the cyclohexane.

EXAMPLE 14

Polymerization of 10,000 MW methacryloxypropyl-terminatedpolydimethylsiloxane macromonomer (PDMS) with N-vinylpyrrolidone (NVP),2-(N-methylperfluorooctane sulfonamido) ethyl acrylate (MeFOSEA), methylmethacrylate (MA), and acrylic acid (AA).

To a mixture of 19 parts of PDMS, 52 parts of MA, 19 parts of NVP, 5parts of AA, and 5 parts of MeFOSEA in 150 parts of methyl ethyl ketonewas added 0.25 parts of azobis(isobutyronitrile). This solution waspurged with nitrogen gas and sealed in a bottle under a nitrogenatmosphere. The bottle was heated in a Launder-O-Meter at 55° C. for 16hours and the polymer was recovered by evaporation of the solvent atatmospheric pressure.

In a separate experiment, to a mixture of 19 parts of PDMS, 43 parts ofMA, 19 parts NVP, 5 parts of AA, and 14 parts of MeFOSEA in 150 parts ofmethyl ethyl ketone was added 0.25 parts of azobis(isobutyronitrile).This solution was purged with nitrogen gas and sealed in a bottle undera nitrogen atmosphere. The bottle was heated in a Launder-O-Meter at 55°C. for 16 hours and the polymer was recovered by evaporation of thesolvent at atmospheric pressure.

EXAMPLE 15

Polymerization of 20,000 MW methacryloxypropyl-termiantedpolydimethylsiloxane macromonomer PPDMS) with iso-butyl acrylate (BA),acrylic acid (AA), and 2-(N-methylperfluorooctane sulfonamido) ethylacrylate (MeFOSEA).

To a mixture of 19 parts of PDMS, 56 parts of BA, 15 parts of AA, and 10parts of MeFOSEA in 150 parts of methyl ethyl ketone was added 0.3 partsof azobis(isobutyronitrile) and 0.13 parts of carbon tetrabromide. Thissolution was purged with nitrogen gas and sealed in a bottle under anitrogen atmosphere. The bottle was heated in a Launder-O-Meter at 55°C. for 54 hours and the polymer was recovered by evaporation of thesolvent at atmospheric pressure.

In a separate experiment, 22 parts of PDMS, 54 parts of BA, 14 parts ofAA, and 10 parts of MeFOSEA in 150 parts of methyl ethyl ketone wasadded 0.3 parts of azobis(isobutyronitrile). This solution was purgedwith nitrogen gas and sealed in a bottle under a nitrogen atmosphere.The bottle was heated in a Launder-O-Meter® at 55° C. for 54 hours andthe polymer was recovered by evaporation of the solvent at atmosphericpressure.

We claim:
 1. A composition comprising:(a) a hydrophobic copolymercomprising repeating A, B, and C monomers wherein:A is at least one freeradically polymerizable acrylic or methacrylic acid ester of1,1-dihydroperfluoroalkanols or homologs of1,1-dihydroperfluoroalkanols, omega-hydridofluoroalkanols,fluoroalkylsulfonamide alcohols, cyclic fluoroalkyl alcohols, andfluoroether alcohols present as up to 99% by weight of all monomerpresent; B is at least one reinforcing monomer copolymerizable with A,the amount by weight of B monomer being from 0.01 to 30% of the totalweight of all monomers in said copolymer; and C is a monomer present asfrom 0.01 to 50% by weight of all monomer present and having the generalformula

    X(Y).sub.n Si(R).sub.3-m Z.sub.m

wherein: X is a vinyl group copolymerizable with the A and B monomers; Yis a divalent linking group; R is hydrogen, lower alkyl, aryl, oralkoxy; Z is a monovalent siloxane polymeric moiety having a numberaverage molecular weight of at least about 5,000 and is essentiallyunreactive under copolymerization conditions; n is zero or 1; m is aninteger of from 1 to 3; and (b) from 0 to about 500 parts by weight ofcompatible solvent or plasticizer per 10 parts copolymer.
 2. Thecomposition of claim 1 wherein at least 75% by weight of saidcomposition comprises said A monomer acrylic or methacrylic acid ester.3. The composition of claim 2 wherein said acrylic or methacrylic acidester is selected from fluorinated compounds of a formula within thegroup consisting of ##STR10## wherein x is 0 to 20, y is 1 to 10, z is 0to 7q is 2 to 20 and greater than x, r is one to 6, p and s are at leastone, and R¹ is alkyl or aryl(alkyl) of up to 20 carbon atoms orcycloalkyl of up to 6 ring carbon atoms.
 4. The composition of claim 1wherein said B is selected from the group consisting of acrylic acid,methacrylic acid, itaconic acid, acrylamide, methacrylamide,N,N-dimethylacrylamide, acrylonitrile, methacrylonitrile, N-vinylpyrrolidone, and macromonomers having a T_(g) or T_(m) above about 20°C., and there is a comonomer D which is a hydrocarbon acrylate ormethacrylate.
 5. The composition of claim 1 wherein said B monomer isselected from a group consisting of acrylic acid, acrylamide,methacrylic acid, N-vinyl pyrrolidone, acrylonitrile, and poly(styrene)macromonomer.
 6. The composition of claim 1 wherein said B monomercomprises about 2% to about 15% by weight of all monomers in saidcopolymer, and there is an additional D comonomer present which is ahydrocarbon acrylate or methacrylate.
 7. The composition of claim 3wherein said X group of said C monomer has the general formula ##STR11##wherein R⁷ is hydrogen or a COOH group and R⁸ is hydrogen, a methylgroup, or a CH₂ COOH group.
 8. The composition of claim 1 wherein said Zgroup of said C monomer has the general formula ##STR12## wherein: R⁹and R¹¹ are independently lower alkyl, aryl, or fluoroalkyl;R¹⁰ isalkyl, alkoxy, alkylamino, aryl, hydroxyl, or fluoroalkyl; and e is aninteger from about 5 to about
 700. 9. The composition of claim 1 whereinsaid C monomer has a general formula selected from the group consistingof ##STR13## wherein R" is alkyl or hydrogen;m is 1, 2 or 3; g is zeroor 1; f is an integer from 2 to 6; h is an integer from 0 to
 2. 10. Thecomposition of claim 1 wherein the molecular weight of said C monomer isin the range of about 10,000 to about 50,000.
 11. The composition ofclaim 1 wherein the molecular weight of said C monomer is in the rangeof about 10,000 to about 25,000, and also present is an additionalcomonomer D which is a hydrocarbon acrylate or methacrylate.
 12. Thecomposition of claim 1 wherein the amount by weight of said C monomer iswithin the range of about 0.01 to about 50% of the total monomer weightin said copolymer.
 13. The composition of claim 1 wherein the amount byweight of said B plus C monomers is within the range of about 5 to about60% of the total weight of all monomers in said copolymer, and alsopresent is an additional comonomer D which is a hydrocarbon acrylate ormethacrylate.
 14. The composition of claim 1 further characterized bybeing crosslinked.
 15. A composition comprising:(a) a hydrophobiccopolymer which comprises repeating A, B, C and D monomers wherein:A isat least one free radically polymerizable acrylic or methacrylic acidester of 1,1-dihydroperfluoroalkanols or methylene homologs of1,1-dihydroperfluoroalkanols, omega-hydridofluoroalkanols,fluoralkylsulfonamide alcohols, cyclic fluoroalkyl alcohols, andfluoroether alcohols present as at least 0.1% by weight of all monomerpresent; B is at least one reinforcing monomer copolymerizable with A,the amount by weight of B monomer being from 0.01 to 30% of the totalweight of all monomers in said copolymer; and C is a monomer present asfrom 0.01 to 50% by weight of all monomer present and having the generalformula

    X(Y).sub.n Si(R).sub.3-m Z.sub.m

wherein: X is a vinyl group copolymerizable with the A and B monomers; Yis a divalent linking group; R is hydrogen, lower alkyl, aryl, oralkoxy; Z is a monovalent siloxane polymeric moiety having a numberaverage molecular weight of at least about 5,000 and is essentiallyunreactive under copolymerization conditions; n is zero or 1; m is aninteger of from 1 to 3; D is at least one free radically polymerizableacrylate or methacrylate monomer; and (b) from 0 to about 500 parts byweight of compatible solvent or plasticizer per 10 parts copolymer. 16.A composition according to claim 1 wherein said A monomer is 2(N-methylperfluorooctane sulfonamido)ethyl acrylate and said C monomer ismethacryloxypropyl-terminated polydimethylsiloxane.